EP0708144B1 - Compositions moulées en fusion contenant de l'alcool polyvinylique - Google Patents

Compositions moulées en fusion contenant de l'alcool polyvinylique Download PDF

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EP0708144B1
EP0708144B1 EP95307439A EP95307439A EP0708144B1 EP 0708144 B1 EP0708144 B1 EP 0708144B1 EP 95307439 A EP95307439 A EP 95307439A EP 95307439 A EP95307439 A EP 95307439A EP 0708144 B1 EP0708144 B1 EP 0708144B1
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core
units derived
weight percent
shell
polymer
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EP0708144A1 (fr
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Jean Marie Brady
Thierry Christian Claude Diaz
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Rohm and Haas Co
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Rohm and Haas Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers

Definitions

  • This invention relates to melt-processed blends of polymers containing a high percentage of vinyl alcohol units blended with certain non-functionalized, non-reactive core/shell copolymers. It further relates to melt-processed blends of these polymers in the form of sheet, film, injection-molded objects, fibers and other formed objects.
  • PVOH poly(vinyl alcohol)
  • R alkyl
  • LaFleur and co-workers have described the unexpected effect of relatively low levels of functionalized "acrylic" additives on the melt-processing of poly(vinyl alcohol).
  • the modifiers of LaFleur et al. have solved many of the problems identified in processing poly(vinyl alcohol), there remains the need for further improvements in melt-processing a wide range of poly(vinyl alcohols) of varying compositions and molecular weights.
  • the functionalized core/shell modifiers can decrease the melt flow index (i.e., make the blend more viscous and harder to process and extrude).
  • the first polymer contains at least 95 mol % units of the "vinyl alcohol” structure, i.e., and most preferably contains 98 % or more of such units.
  • the optional units in the vinyl alcohol copolymers are preferably those derived from ethylene or vinyl acetate.
  • the first polymer preferably should exhibit a low content of acetate ions, such as sodium acetate.
  • the sodium content (or general salt content) may be measured with a Varian AA 300 Atomic Absorption Spectrometer or a similar device. The content may be low as received from the supplier, or it may be decreased by washing the first polymer, or the acetate content may be lowered by treatment with phosphoric acid, as in U. S. Patent 3,425,979, which converts the acetate to acetic acid, which is vented during the melt processing.
  • the rubbery, crosslinked core preferably contains at least 75 weight percent, preferably at least 95 weight percent, of units derived from butadiene or from butyl acrylate. Units derived from other alkyl acrylates, styrene, or acrylonitrile are preferably at levels of 5 weight percent or less. It is generally preferred to have present one or more polyunsaturated monomers other than butadiene, and the preferred amount is from 0.5 to 2 weight percent.
  • the polyunsaturated monomers may contain two or more sites of unsaturation of equivalent reactivity, as illustrated by ethylene glycol dimethacrylate, trimethylolpropane triacrylate, divinylbenzene, and the like, or may contain two or more sites of unequal reactivity, as illustrated by allyl methacrylate, diallyl maleate, and the like.
  • intermediate shells it is not necessary that one or more intermediate shells be present, but some commercially available core/shell impact modifiers, designed for modification of other thermoplastics such as poly(vinyl chloride) or poly(ethylene terephthalate) and the like, may contain such intermediate shells.
  • the additive may be added in emulsion form and the water removed by evaporation during the compounding process, by such means as evaporation or vacuum devolatilization.
  • glycerol may lower the glass temperature of the final blend, it can aid in obtaining better admixture of the two components, so as to avoid presence of gel or requirement of extensive melt-mixing.
  • the core or shell(s) of the core/shell modifier useful in the present invention do not contain units derived from a copolymerizable monomer containing amide or cyclic amide functionality, so that the modifier does not contain, e.g., units derived from vinyl pyrrolidone, (meth)acrylamide, N-vinyl acetamide, and the like.
  • the core/shell modifier does not contain reactive functionality, that is, does not contain units derived from a functional monomer capable of reaction with the hydroxyl groups of the first polymer, such as glycidyl methacrylate, methacrylic acid, acrylic acid, maleic anhydride, and the like.
  • core/shell polymers known to be useful as processing aids for poly(vinyl chloride), are surprisingly useful for obtaining melt-processed poly(vinyl alcohol).
  • core/shell polymers differ from the core/shell impact modifiers described previously, in that the core is: (a) not cross-linked; (b) not necessarily rubbery in nature; (c) present at a lower level, usually 10 to 60 weight percent of the total modifier, than in an impact modifier, where the core is 60 - 90 % of the total modifier.
  • a melt-processed blend comprising:
  • Typical of such polymers which can readily be prepared by emulsion synthesis using well-known techniques of staged addition of monomers under conditions where no new particles are formed and the second or "shell" polymer is formed at or near the surface of the core particles.
  • Illustrative of such modifiers is a core/shell polymer of 50-60 parts of poly(butyl acrylate/styrene/methyl methacrylate (78/18/4) core // 40 - 50 parts of methyl methacrylate/butyl acrylate/styrene (92/4/ 4) wherein the molecular weight of the core is kept below ca. 300,000 daltons by the presence of n-dodecyl mercaptan; such polymers are taught in Carty et al.
  • a second type of polymer illustrative of such modifiers is a core of poly(ethyl acrylate) 25 parts// 75 parts of a shell of methyl methacrylate/ethyl acrylate (75/25), the shell being of MW ca. 700,000 daltons, the first stage preferably having a glass temperature below 60 °C., as taught in Grochowski et al. , U. S. Patent 3,833,686.
  • Neither patent teaches or suggests the utility of such core/shell polymers for preparing a melt-processed blend of poly(vinyl alcohol).
  • the first polymer in such blends may be a blend of more than one polymer containing vinyl alcohol units, such as those of differing molecular weight.
  • the first polymer, containing vinyl alcohol units may be washed or be neutralized with acid such as phosphoric acid to remove residual sodium acetate, as taught in U. S. Patent 3,425,979.
  • acid such as phosphoric acid
  • the art teaches that sodium acetate from the alkaline hydrolysis of the copolymerized vinyl acetate accelerates the formation of conjugated species and chemical cross-links upon heating the polymer containing vinyl alcohol units to within a few degrees of its melting temperature.
  • the acid treatment is used, the acetic acid formed is removed in the extrusion process by appropriate venting. In both treatments, essentially all of the sodium acetate is removed, so that the content of sodium acetate is less than about 0.1 wt. percent, based on the polymer containing vinyl alcohol.
  • Blending of the two polymers may be carried out most conveniently by dry mixing the finely granulated polymer particles prior to melt compounding in a single-or twin-screw extruder.
  • additives may include one or more of the following classes of compounds: antioxidants, ultraviolet light absorbers, plasticizers, antistatic agent, slip agents, coloring agents, fillers and other compounds.
  • fugitive plasticizers such as water in amounts about 3%, may be added to aid in compounding and processing the blend.
  • the blend containing the non-crosslinked acrylic additive may further be prepared by admixing the additive polymer in emulsion form, when an emulsion polymerization is a feasible way to prepare the additive polymer, with the poly(vinyl alcohol) in solid form, and then processing directly with water removal such as by extrusion in a vented extruder, or by drying the powder blend under vacuum, and then blending with the matrix polymer.
  • the blend may further contain glycerol in small amounts. Although glycerol may lower the glass temperature of the final blend, it can aid in obtaining better admixture of the two components, so as to avoid presence of gel or requirement of extensive melt-mixing.
  • the blend may further contain functionalized impact modifiers known to the art, such as multistage polymers based on a poly(acrylate) first stage or a polybutadiene first stage and a methacrylate or styrene second stage, which may be present as a shell or in separate domains within the core, and where at least one stage will contain acid-functional groups, or other reactive sites, such as glycidyl groups.
  • functionalized impact modifiers known to the art, such as multistage polymers based on a poly(acrylate) first stage or a polybutadiene first stage and a methacrylate or styrene second stage, which may be present as a shell or in separate domains within the core, and where at least one stage will contain acid-functional groups, or other reactive sites, such as glycidyl groups.
  • the blends of the present invention may be considered as a polymer containing vinyl alcohol units modified with a processing aid, since the acrylic copolymer additive enables the poly(vinyl alcohol) to be melt-processed with a reduced tendency towards thermal decomposition, and aids in the formation of melt-processable objects or melt-processable intermediates, such as pellets.
  • blends in many applications are useful in many applications.
  • a film from the blends can be broken down in water for ready disposal.
  • Such blends in film form may also be useful as containers for toxic, corrosive, or skin-sensitizing chemicals which are to be used in water, such as agricultural chemicals to be sprayed.
  • the blends in film form such as in blown film, are useful as high gas barrier films for packaging, especially of food.
  • the films from the blends can be laminated onto substrates to form useful barrier structures for containment or packaging of food or beverages.
  • the blends in container form, such as film, bottles, and the like may be used to exclude gases such as oxygen or to contain gases such as carbon dioxide.
  • Blends with improved heat distortion properties may be useful in hot fill packaging or in retortable or sterilizable container packaging.
  • the blends or laminates may also be useful in museum and other glazing where clarity and long-term retention of an inert atmosphere are desired.
  • the blends may also be useful in bags for medical laundry, and for lamination of films to paper.
  • the blends of the present invention may be used to form useful fibers.
  • the blends may be processed from the melt or from a solvent-swollen gel.
  • the melt-processable blends may be passed through an appropriate die to form filaments which may be stranded into single or multi-stranded fibers of various thicknesses.
  • the fibers may then be further processed into appropriate products, such as packaging materials, water-soluble disposable cloths, such as diapers, and the like.
  • the fibers may be post-treated after forming by chemicals which will insolubilize the poly(vinyl alcohol), and the resulting fibers may be processed into articles with high moisture uptake which do not dissolve in water. Further, the polymers may be spun by a solid state process wherein the fiber is oriented in the solid state to produce a fiber with a very high tensile modulus.
  • Films from the present blends may be laminated, co-extruded, or co-injection molded to form laminated structures with a good combination of clarity, toughness, and barrier properties.
  • a blend may be co-extruded with poly(ethylene terephthalate) (PET), with poly(methyl methacrylate), with poly(vinyl chloride), or with polycarbonate, to form continuous laminated film with good adhesion between the layers.
  • PET poly(ethylene terephthalate)
  • the co-extruded film with PET can be thermoformed into useful objects without delamination. Multi-layer laminates may also be formed.
  • the blends may also be injection-molded into useful objects. It should be noted that at additive levels below 6 parts, any external lubricant, such as polyethylene wax, should be avoided or used at lower levels than those shown for mill-mixed or calendered formulations, so that adequate fusion will be obtained in the extruder compounding prior to injection molding.
  • any external lubricant such as polyethylene wax
  • the blends are also suitable for calendering, profile extrusion, foam extrusion, and extrusion blow molding into useful articles, either in film or as thicker articles.
  • Viscosity measurements are by DIN 1342 using a capillary viscometer DIN 52562 and DIN 53012. Trade Name Designation Supplier % PVOH Visc., 4 % mPa s MP, °C Mowiol 010-98 Hoechst 98 7.7 226 ELVANOL 9050 DuPont 98 12.4 226 AIRVOL 107 Air Products 98 5.23 223 AIRVOL 710 Air Products 98 8.2 220 AIRVOL 6108 Air Products 88 6.9 175 Rhodoviol 008/20 Rhone Poulenc 88 3.53 177 Rhodoviol 004/125 Rhone Poulenc 98 8.64 220
  • Additive A A core/shell (75//12.5// 12.5) polymer of a butadiene/styrene 95/5 rubber (with 1 % divinylbenzene)// styrene // methyl methacrylate/butylene glycol dimethacrylate (99/1); stabilized with a combination of hindered phenol antioxidants and tris(nonylphenyl)phosphite. This additive is in within the present invention.
  • Additive B A core/shell (70//30)polymer of a butadiene/styrene 95/5 rubber (with 1 % divinylbenzene)// methyl methacrylate/ butyl acrylate/ methacrylic acid (60/30/10); stabilized with a combination of hindered phenol antioxidants as taught in U. S. Patent 5,164,434. This additive is not within the present invention.
  • Additive C Tetrapolymer of methyl methacrylate 55/ ethyl acrylate 10/ N-vinylpyrrolidone 25/ methacrylic acid 2 of MW ca. 50,000, prepared by methods similar to that of Example 37 of U. S. Patent 5,189,097. This additive is not within the present invention.
  • Additive G A core/shell (80//20) polymer of a butyl acrylate/ trimethylolpropane triacrylate/ allyl methacrylate (99/0.5/0/5) rubber //methyl methacrylate (100) containing 1 % calcium stearate-coated calcium carbonate. This additive is within the present invention.
  • Processing Aid E a butyl acrylate/styrene (82/18)// methyl methacrylate core/shell (50/50) copolymer, non-crosslinked.
  • Antioxidant F tetrakis(methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)) methane
  • Test Procedures The Brabender Plasticorder is used for compounding. Typical compounding conditions are 70 RPM speed, 210 °C setting temperature, with variable mixing times. A pre-blend of PVOH and additive in powder form is placed in the mixing bowl. Fusion is judged visually, as is color development.
  • Some formulations compounded on the Werner-Pfleiderer are then injection molded on an Arburg 50T injection-molding machine.
  • a mold designed for crystalline resins is used; it has 7 cavities, including a plaque of size 8 x 10 x 0.32 cm.
  • the barrel temperature is 230 °C. and the mold temperature 100 °C.
  • EXAMPLE 1 This Example demonstrates the ability of Additive A to cause melt fusion of the blend with a poly(vinyl alcohol) with results very similar to a functionalized additive taught by LaFleur et al., and with improved fusion results under these test conditions over a tetrapolymer composition also taught as effective by LaFleur et al. Melt flow rates are reported after 1 minute and two minutes of processing; flow temperature is 270 °C. Note Additive A exhibits significantly better flow than the functionalized core/shell copolymer (Additive B). Formulation Ex. 1A Ex. 1B Ex. 1C Ex.
  • EXAMPLE 3 This Example exhibits the improved processing in a twin-screw extruder over one of the additive polymers taught by LaFleur.
  • the product In all extrusions, the product is cooled with air, the RPM of the extruder is 150 RPM, and the temperature setting over five zones is (in degrees C.) 235/230/225/225/245 at a feed of 7 kg./hour.
  • Formulation 3-A is tried first. Fusion occurs and a white product is obtained. The final zone temperature could be lowered to 225 °C. with production of white pellets.
  • Formulation 3-B With formulation 3-B at 235/ 230/225/225/225, good fusion is obtained.
  • Formulation 3-C does not fuse over a range of processing conditions, although in a separate experiment under conditions similar to Example 3-B, fusion was observed. The reason for the non-reproducibility is unknown.
  • Formulation Ex. 3A Ex. 3B Ex. 3C Mowiol 10-98 87.9 91.8 87 Additive A 9.9 6 Additive C 10.3 Wax D 1.6 1.7 Processing Aid E 0.6 0.6 H3PO4 0.06 Antioxidant F 0.54 Glycerol 10
  • EXAMPLE 4 This Example demonstrates that Additive A is less prone to cause good fusion and avoid burning than Additive B in a PVOH of similar molecular weight and degree of hydrolysis, but of higher residual acid content, although it is of equivalent effectiveness to Additive C, as taught by LaFleur. It should be noted that these formulations (Examples B and C) contain quite high levels of wax, which, although preventing sticking, may have contributed to poorer mixing and thus poorer fusion. Formulation Ex. 4A Ex. 4B Ex. 4C Ex.
  • EXAMPLE 9 This Example illustrates the ability of a core/shell polymer with a non-crosslinked core to be combined with poly(vinyl alcohol) to yield a melt-processable blend.
  • a blend of PVOH of approximately equal weight of ELVANOL 9050 and AIRVOL 107 (80 parts) is admixed with 10 parts of glycerol and 10 parts of an acrylic core-shell modifier with a core of poly(ethyl acrylate) 25 parts and 75 parts of a shell of methyl methacrylate/ ethyl acrylate (75/25), the shell being of MW ca. 700,000 daltons, prepared in emulsion as taught in U. S. Patent 3,833,686, and isolated by spray-drying.
  • the blend may be processed in equipment such as a single-stage Killion extruder a single screw Killion extruder at temperatures of 200 to 216°C to yield a melt-processable blend which could be pelletized.
  • the resultant blend may be re-processed in a similar extruder equipped with an appropriate die and blow-up equipment to yield a coherent thin film.
  • EXAMPLE 10 This Example illustrates the ability of a core/shell polymer with a cross-linked core of an alkyl acrylate rubber to yield a melt-processable blend.
  • the formulation of Example 1-B is utilized, but Additive G replaces Additive A.
  • the mixture of powders is compounded on a two-mill roll set at 230 °C. Fusion occurs after 45 seconds.
  • the melt-processed blend is readily removed from the mill in the form of a thin film. From experience with similar films, it is fully expected that the resulting film could be calendered on conventional equipment into a useful packaging film of uniform thickness.
  • EXAMPLE 13 This Examples illustrates that a core/shell polymer based on an butyl acrylate rubbery core.
  • a blend of Mowiol 10-98 poly(vinyl alcohol) 90 parts, Additive G 10 parts, Wax D, 2.4 parts, and Processing Aid E 0.72 parts is blended on a two-roll mill at a roll temperature of 230 °C. and a speed of 26 rpm. Fusion time is 30 - 45 seconds.
  • the rolling bank is smooth, there is good resistance to sticking to the mill, and the blend color is white. By visual observation, the melt strength is adequate for further processing, such as calendering.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Paper (AREA)
  • Graft Or Block Polymers (AREA)

Claims (2)

  1. Mélange mis en oeuvre à l'état fondu, comprenant :
    a) de 80 à 98 parties d'au moins un premier polymère contenant au moins 80 % en moles de motifs de structure
    Figure 00230001
    et éventuellement des motifs choisis parmi une ou plusieurs des structures suivantes : - CH2 - CH2 - ;   - CH2 - CHR - ;
    Figure 00230002
    où R est le groupe méthyle, R1 est H ou CH3, et R2 est un groupe alkylènoxy ; et
    b) de 2 à 20 parties d'un modifiant coeur/gaine comprenant
    (b.1) un modifiant coeur/gaine réticulé, comprenant :
    (1) de 60 à 90 parties d'un coeur réticulé caoutchouteux, comprenant :
    (i) au moins 75 % en poids de motifs qui dérivent d'au moins l'un des composés butadiène ou acrylate d'alkyle dont le groupe alkyle contient de 2 à 8 atomes de carbone ;
    (ii) éventuellement, jusqu'à 25 % en poids de motifs qui dérivent d'au moins l'un des composés acrylate d'alkyle dont le groupe alkyle contient de 1 à 8 atomes de carbone, styrène ou acrylonitrile ;
    (iii) éventuellement, jusqu'à 5 % en poids de motifs qui dérivent d'au moins un monomère polyinsaturé autre que le butadiène ;
    (2) éventuellement, jusqu'à 15 parties d'une ou plusieurs gaines intermédiaires comprenant :
    (i) au moins 51 % en poids de motifs qui dérivent du styrène ;
    (ii) éventuellement, jusqu'à 49 % en poids de motifs qui dérivent d'au moins un (méth)acrylate d'alkyle dont le groupe alkyle contient de 1 à 8 atomes de carbone ;
    (iii) éventuellement, jusqu'à 5 % en poids de motifs qui dérivent d'au moins un monomère polyinsaturé ;
    (3) de 10 à 40 parties d'une gaine finale comprenant :
    (i) au moins 51 % en poids de motifs qui dérivent du méthacrylate de méthyle ;
    (ii) éventuellement, jusqu'à 49 % en poids de motifs qui dérivent d'au moins l'un des composés styrène ou méthacrylate d'alkyle autre que le méthacrylate de méthyle et dont le groupe alkyle contient de 1 à 8 atomes de carbone ;
    (iii) éventuellement, jusqu'à 5 % en poids de motifs qui dérivent d'au moins un monomère polyinsaturé ; et/ou
    (b.2) un polymère coeur/gaine non-réticulé, comprenant :
    (1) de 10 à 60 parties d'un coeur non-réticulé comprenant au moins 75 % en poids de motifs qui dérivent d'au moins un acrylate d'alkyle dont le groupe alkyle contient de 2 à 8 atomes de carbone ;
    (2) de 40 à 90 parties d'une ou plusieurs gaines comprenant au moins 70 % en poids de motifs qui dérivent du méthacrylate de méthyle ;
       où aucun composant du coeur ou de la gaine du modifiant coeur/gaine ne contient de motifs qui dérivent d'un monomère fonctionnel capable de réagir avec les groupes hydroxyle du premier polymère, et où aucun composant de coeur ou de gaine du modifiant coeur/gaine ne contient de motifs qui dérivent d'un monomère copolymérisable contenant des groupes amide ou amide cyclique.
  2. Mélange mis en oeuvre à l'état fondu selon la revendication 1, dans lequel le premier polymère contient au moins 88 % en moles de motifs de structure
    Figure 00250001
    et dans lequel la viscosité d'une solution aqueuse à 4 % du premier polymère est d'au moins 4 mPa.s, et la teneur en acétate du premier polymère est inférieure à 0,88 %.
EP95307439A 1994-10-20 1995-10-18 Compositions moulées en fusion contenant de l'alcool polyvinylique Expired - Lifetime EP0708144B1 (fr)

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Application Number Priority Date Filing Date Title
FR9412553A FR2725999A1 (fr) 1994-10-20 1994-10-20 Melanges a mettre en oeuvre a l'etat fondu renfermant de l'alcool polyvinylique
FR9412553 1994-10-20

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JP (1) JPH08225703A (fr)
KR (1) KR960014236A (fr)
CA (1) CA2160956A1 (fr)
DE (1) DE69518711T2 (fr)
FR (1) FR2725999A1 (fr)
TW (1) TW314537B (fr)

Cited By (2)

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US7426775B2 (en) 2003-12-17 2008-09-23 The Procter + Gamble Company Polymeric structures comprising a hydrophile/lipophile system
US7714065B2 (en) 2003-12-17 2010-05-11 The Procter & Gamble Company Polymeric structures comprising a hydrophile/lipophile system

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FR2745582A1 (fr) * 1996-03-01 1997-09-05 Rohm & Haas France Melange mis en oeuvre a l'etat fondu contenant un poly(alcool vinylique) pour obtenir notamment des objets moules
US5753752A (en) * 1997-02-07 1998-05-19 Rohm And Haas Company Melt-processed blends containing poly(vinyl alcohol)
US6638636B2 (en) 2001-08-28 2003-10-28 Kimberly-Clark Worldwide, Inc. Breathable multilayer films with breakable skin layers
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7426775B2 (en) 2003-12-17 2008-09-23 The Procter + Gamble Company Polymeric structures comprising a hydrophile/lipophile system
US7714065B2 (en) 2003-12-17 2010-05-11 The Procter & Gamble Company Polymeric structures comprising a hydrophile/lipophile system
US8071203B2 (en) 2003-12-17 2011-12-06 The Procter & Gamble Company Polymeric structures comprising a hydrophile/lipophile system
US8137797B2 (en) 2003-12-17 2012-03-20 The Procter & Gamble Company Polymeric structures comprising a hydrophile
US8241738B2 (en) 2003-12-17 2012-08-14 The Procter & Gamble Company Polymeric structures comprising a sulfosuccinate
US8445100B2 (en) 2003-12-17 2013-05-21 The Procter & Gamble Company Polymeric structures comprising a sulfosuccinate
US8709585B2 (en) 2003-12-17 2014-04-29 The Procter & Gamble Company Polymeric structures comprising a siloxane
US9103051B2 (en) 2003-12-17 2015-08-11 The Procter & Gamble Company Polymeric structures comprising a sulfosuccinate

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DE69518711T2 (de) 2001-05-23
EP0708144A1 (fr) 1996-04-24
CA2160956A1 (fr) 1996-04-21
TW314537B (fr) 1997-09-01
KR960014236A (ko) 1996-05-22
JPH08225703A (ja) 1996-09-03
FR2725999A1 (fr) 1996-04-26
DE69518711D1 (de) 2000-10-12

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